反应详情

温度

190 °C

To a one liter stainless steel autoclave equipped with a mechanical stirrer, thermometer, and a gas inlet tube were placed 50.0 grams (0.20 mole--1.0 equiv.) of the sodium salt of 4,5-dihydro-1-(4-chloro-2-fluorophenyl)-3-methyl-5-oxo-1H-1,2,4-triazole and 13.8 grams (0.10 mole--0.5 equiv.) of solid potassium carbonate in 500 mL (% wt/vol. triazole to solvent--10.0%) of diglyme. The autoclave was sealed, and the reaction mixture was warmed to 190° C. Upon reaching 190° C. the reaction vessel was vented to expel water and carbon dioxide. The reaction vessel was resealed, and 34.6 grams (0.40 mole 2.0 equiv.) of chlorodifluoromethane was bubbled in below the surface of the reaction mixture. The pressure in the autoclave following the addition of chlorodifluoromethane was about 64 psi. Upon completion of the addition the reaction mixture was maintained at 190° C. for about 30 minutes, after which the reaction mixture was cooled to ambient temperature, the autoclave was opened, and the reaction mixture was then poured into 1500 mL of water. The autoclave was rinsed with N,N-dimethylformamide, and the rinse was also added to the 1500 mL of water. The mixture was stirred vigorously for two hours, and the solid product was collected by filtration. The filter cake was washed with five 300 mL portions of water and air-dried to a constant weight, yielding 52.3 grams of 95.0% pure 4-difluoromethyl-4,5-dihydro-1-(4-chloro-2-fluorophenyl)-3-methyl-5-oxo-1H-1,2,4-triazole (89.4% yield). GC analysis of the product indicated the presence of <0.5% 0-isomer by-product.

1. customthermometer, and a gas inlet tube were placed
2. customThe autoclave was sealed
3. customUpon reaching 190° C.
4. additionUpon completion of the addition the reaction mixture
5. temperaturewas maintained at 190° C. for about 30 minutes
6. temperatureafter which the reaction mixture was cooled to ambient temperature
7. washThe autoclave was rinsed with N,N-dimethylformamide
8. additionthe rinse was also added to the 1500 mL of water
9. filtrationthe solid product was collected by filtration
10. washThe filter cake was washed with five 300 mL portions of water
11. customair-dried to a constant weight